Alkali metal-dimethyl dodecyl amine salts of oxyacids of phosphorous and sulfur



United States Patent Ofilice 3,308,161 Patented Mar. 7, 1967 This invention relates to inorganic amine salts of oxyacids of phosphorus and chalcogens having a molecular weight greater than 16, i.e. S, Se, Te (also referred to herein generally as oxyacids).

More particularly this invention relates to salts of (1) Oxyacids of sulfur and (2) oxyacids of phosphorus wherein the salts contain both an inorganic and an amine cation. Still more particularly this invention relates to salts of inorganic acids for example (1) sulfurous, sulfuric, etc. acids and (2) phosphorous, phosphoric, etc. acids which contain both an amine and an inorganic cation.

In general, these salts are prepared by neutralizing with an amine an inorganic salt of an oxyacid having at least one acidic hydrogen This reaction is illustrated by the following equations:

where R is hydrogen or a substituted group, such as a hydrocarbon group, alkyl, alkenyl, aryl, alkaryl, aralkyl, hydroxyalkyl, hydroxyoxyalkyleneetheralkyl, acylated and etherified derivatives of said hydroxy compounds, etc

Analogous salts can also be prepared from other amines such as polyamines, heterocyclic amines, etc. for example,

69 g [69 G3 1% G9 NaSOa NHa-CHzCHzNI-Ie, SOBNB Oxyacids of phosphorous:

H PO (phosphorous acid) H PO (phosphoric acid), and the like. Oxyacids of sulfur:

H 80 (sulfurous acid) H 80 (sulfuric acid), and the like.

Analogous oxyacids of selenium can also be employed for example H SeO H SeO etc.

In the compounds of this invention at least one of the hydrogens of the oxyacids is combined with the amine.

Thus, the salts of this invention contain at least one amine group and at least one inorganic cation. The remaining acid hydrogens may be unreacted or reacted to form either an inorganic or an amine cation. The inorganic cation is preferably an alkali metal.

In general, any basic amine capable of forming a salt with the oxyacid can be employed. The following are non-inclusive examples:

I. Monoamirzes A. Primary m0n0amines.-These include compounds of the formula RNH where R is a substituted group preferably a hydrocarbon group, for example alkyl, cycloalkyl, aryl, alkenyl, heterocyclic, substituted derivatives of the above, etc.

ALKYL Alkyl includes methyl, ethyl, propyl, butyl, amyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, eicosyl, docosyl, etc. having 1-50 or more carbons, such as 130, but preferably l-l8 carbons.

The term alkyl also includes isomers of the straight chain group wherein branching occurs along the chain, for example ALKENYL AND ALKINYL These include unsaturated analogues of alkyl groups containing one or more groups, for example decenyl, dodecenyl, tridecenyl, tetradecyl, pentadecenyl, hexadecyl, heptadecenyl, octadecenyl, etc., dienes for example octadienyl, etc. trienes, for example octatrienyl, etc., alkinyl, for example, butinyl, etc.

CYCLOALKYL These include for example cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, etc.; substituted derivatives there-of, for example alkyl or polyalkyl, for example alkyl cyclohexyl, dialkyl cyclohexyl, etc.

ARYL

These include phenyl, substituted phenyl, alkyl phenyl, polyalkylphenyl, chlorophenyl, alkoxyphenyl, etc., naph thyl, alkyl naphthyl, etc.; benzyl, substituted benzyl, etc. groups.

HETEROCYCLIC These include furyl, pyranyl, hydrogenated furyl, pyranyl, etc. groups.

B. Secondary amines.These include amines of the formula R-ZII-H RI where R and R, which may or may not be the same,

have the same meaning as stated above, for example dimethyl amine, diethyl amine, dipropyl amine, di'arnylamine, di-hexyl amine, dioctyl amine, didodecyl amine, dihexyldecyl amine, etc., methyl ethyl amine, met-hyl octyl amine, butyl octylamine, methyl octadecyl amine, etc.; methyl octadecenyl amine, dioctadecenyl amine, etc.; dicyclohexyl amine, methyl cyclohexyl amine, etc.; methyl furyl amine, methyl benzyl amine.

C. Tertiary amines.These include amines of the formula where the R's, which may or may not be the same, have the same meaning as stated above, for example, trimethyl amine, triethyl amine, dimethyl octyl, dimethyl dodecyl, dimethyl tetrradecyl, diethyl hexadecyl, methyl ethyl octadecyl, dimethyl octadecyl, etc., dimethyl octadecenyl, diethyl hexadecenyl, etc. dodcyl benzyl methyl, decyl di- 4 naphthyl, etc., dicyclohexyl methyl, dimethyl cyclohexyl, etc.

D. Commercial amines.-R,epresentative commercial amines are available, for example, these shown in the following tables.

The nomenclature of these amines is derived from either their chain length or source of raw material, for example,

Armeen 8D-octyl amine Armeen C-coconut oil amine Armeen S-soybean oil amine Armeen TtallW amine Armeen O-oleyl amine Armeen HT--hydrogenated tallow amine Armeen DMCD-dihydrogenated tallow amine Armeen M2HT-dimethyl coconut oil amine.

Products with D designate distilled grade. Products benzyl, etc.; dimethyl furyl, etc., dimethyl phenyl, diethyl 20 Without D designate technical grade.

TABLEI Primary Second- Diamines Carbon Q Q N-alk lChain Chain Q Q Q Q a a a a o a 0 o E y aueaammeeeemfioogEaafi ceeeceeeeeeeecccec eaeaeaaeasaaaaeaeefi Efi l i i t i t i i i i d i i i i iQQQQ Hexyl Octyl- 8 8 8 DecyL- 9 9 9 DodecyL- 47 47 47L"- TetradecyL 18 18 18 Hexadecyl 8 8 8124 Octadecyl 5 75 Octadecenyl 5 5 1 Octadecadienyl 18 M01. combining wt 135 166 213 195 227 250 300 275 300 280 298 274 297 275 223 208 450 530 321 310 402 400 PrimaryAmine 82 94 92 95 85 95 85 95 85 95 86 95 85 95 40 44 40 40 SecondaryAmine .0. 85 85 Approx. Melting Pt.,C 8 24 24 29 38 57 55 55 46 31 22 24 46 68 22 46 Color-FAG 3 9 3 3 3 11 3 11 3 11 3 19 7 11 3 9 5 19 11 13 19 Grade: D-Distilled, TTechnical D T D D D T D T D T D T D T D D D T D T T TABLE II Dimethyl Tertiary Amine Dialkyl Tertiary Amines Carbon Q a Q E a N-alkylChain ohamfifiezoom mmfi Length 2 2 E Q 2 2 2 2 2 2 E or or Q Q Q Q Q Q Q Q Q 2 2 2' aaaaaaaaaaaaa 1 4 5 1 3 1 4 1 1 1 1 1 1 Hexyl 6 Octyl 8 Decy1 10 Dodecyl 12 Tetradecyl. 14 HexadecyL- 16 OetadecyL 18 0ctadeceny1 18 Octadeeadienyl 18 M01. weighttheoret1cal M01. combining weight. Percent Tertiary Amine Approx. Melting PL, C. Color-Gardner-1933 DDisti1led, T-Teelmical.

Other commercial amines include the following: Primene amines Rosin Amine D (11 H HzNHg etc.

E. Cyclic secondary and tertiary amines.Also included within the definition of secondary and tertiary amines are those amines where two of the R groups are joined in a cyclic structure such as Examples of these amines include pyridine, quinoline, isoquinoline, acridine, piperidine, piperazine, morpholine, etc. Certain N-substituted derivatives thereof, such as N-alkyl morpholine, N-alkyl piperidine, N-alkyl piperazine, etc., for example N-dodecylmorpholine, N-octadecylmorpholine, N-dodecylbenzylmorpholine, N-nonylmethylbenzylmorpholine, N-cetylpiperidine, Octylphenoxyethoxyethylmorpholine, Nonylphenoxyethoxyethylpiperidine,

(R and R=alky1, alkenyl, hydrogen, etc.)

II. Polyamz'nes These include polyamines corresponding to the formula in which R" (which may or may not be the same) is hydrogen, alkyl, cycloalkyl, aryl, or aralkyl and R is a divalent radical such as etc.

Ethylenediamine Diethylenetri-amine Triethylenetetramine Tetraethylenepentamine Propylenediamine Dipropylenetriamine Tripropylenetetramine Butylenediamine Aminoethylpropylenediamine Aminoethylbutylenediamine R is an alkyl group derived from a fatty acid or from the mixed fatty acids as obtained from certain oils. The specific Duomeen and the source of the radical R are as follows:

(1) Duomeen 12, R=1auric (2) Duomeen C, R=coconut oil fatty acid (3) Similarly, a comparable diamine, obtained from Rosin Amine D and acrylonitrile, can be prepared.

CH CH3 Additional examples of polyamines include the followmg:

H CuHzq-N-C Hz C Hr-NHg N-tetradecyl ethylenediamine H ClaHza-N- C Hg-C HzNH2 -N-hexadecylethyleuedizuuiue H C1zH25NCaHo- H2 tN-dodecyl propylenedi'amine Diamines containing tertiary amino groups for example It is to be noted that the above examples show high molal groups, i.e., 8 carbon atoms or more. The same derivatives in which methyl, ethyl, propyl, butyl, amyl, hexyl groups, or the like, appear instead of octyl, decyl, etc., are equally satisfactory.

Acylated polyamines can also be employed provided they'are sufiiciently basic to form salts, for example:

H H AbietylC-N-OHzC HzNHz III. Cyclic amidines atom of the ring, involving monovalent linkages (the 1- position), may be unsubstituted or substituted for example, an alkylene amine group, a polyalkylene amino group, an alkylene hydroxyl group, a polyoxyalkylene hydroxy group, an alkylenethiol group, a polythioalkylenethiol group, a polyalkylene group containing both sulfur and oxygen, nitrogen and oxygen, nitrogen, sulfur and oxygen, etc.

These cyclic amidines are further characterized as being substituted imidazolines and tetrahydropyrimidines in which the two-position carbon of the ring is generally bonded to a hydrocarbon radical or comparable radical derived from an acid, such as a low molal fatty acid, a high molal fatty acid, or comparable acids, aromatic acids, polycarboxy acids, acids containing heterocyclic rings, and the like.

For details of the preparation of imidazolines from amines, see the following US. patents, US. No. 1,999,- 989 dated Apr. 30, 1935, Max Bockmuhl et al.; US No. 2,155,877 dated Apr. 25, 1939, Edmund Waldmann et al.; and US. No. 2,155,878 dated Apr. 25, 1939, Edmund Waldman et al. Also see Chem. Rev. 32, 47 (43), Chem. Rev. 54, 593 (54), and Imidazole and Derivatives, I by K. Hofmann (1953).

Equally suitable for use in preparing compounds useful in this invention and for the preparation of tetrahydropyrimidines substituted in the 2-position are the corresponding polyamines containing at least one primary amino group separated from the first primary amino group by three carbon atoms instead of being separated by only 2 carbons as with imidazolines. This reaction, as in the case of the imidazolines, is generally carried out by heating the reactants to a temperature at which 2 moles of water are evolved and ring closure is effected. For details of the preparation of tetrahydropyrimidines, see German Patent No. 700,371 dated Dec. 18, 1940, to Edmund Waldmann and August Chwala; German Patent No. 701,322 dated Jan. 14, 1941, to Karl Kiescher, Ernst Urech and Willi Klarer, and US. Patent No. 2,194,- 419 dated Mar. 19, 1940, to August Chwala.

Substituted imidazolines and tetrahydropyrimidines are obtained from a variety of acids beginning with the onecarbon acid (formic) through and includnig higher fatty acids or the equivalent having 1-30 or more carbon atoms such as from 8-22 carbons. Modified fatty acids also can be employed as, for example, phenyl stearic acid or the like. Cyclic acids may be employed, including naphthenic acids. A variety of other acids, including benzoic acid, substituted benzoic acid, salicyclic acid, and the like, have been employed to furnish the residue from the acid RCOOH in Which the C of the residue is part of the ring. The fatty acids employed, for example, may be saturated or unsaturated. They may be hydroxylated or non-hydroxylated. Branched long chain fatty acids may be employed. See J. Am. Chem. Soc. 74, 2523 (1952). Thisapplies also to the lower molecular weight acids as well.

As is well known, cyclic amidines containing in the 1-position a substituted group can be prepared by reacting a suitable amine with the desired carboxylic acid under suitable conditions so as to remove 2 moles of water for each equivalent of carboxylate radical. Thus, where one employs a diamine such as ethylene or propylene diamine, a cyclic amidine which is unsubstituted in the 1-position is obtained. This compound can be reacted with such compounds as alkylene oxides, alkylene where Z is the residuum of the cyclic amidine ring, derived from the cyclic amidine forming polyamine, R is the group derived from the carboxylic acid, and A is alkylene, X is oxygen, amino, sulfur, etc. and n is a number for example 1-10 or higher.

Alternatively amino and polyamino substituted cyclic amidine compounds can be prepared from polyamines such as a triamine or higher amines, for example, diethylene triamine, triethylene tetraethylene pentamine, corresponding propylene analogues, etc. Thus, when one reacts diethylene triamine with a carboxylic acid or its esters, one obtains and with triethylene tetramine one obtains It should be noted that Z can also be part of an aromatic ring. Thus, by reacting with a carboxylic acid one obtains Hydroxy-substituted imidazolines and tetrahydropyrimidines can be obtained in the manner described above from a Wide variety of polyamines containing hydroxy groups. Thus, where one starts with a polyamine, for example, a diamine of the following formula:

Where Z and Z have a 2 or 3 carbon chain in the main chain, one obtains the hydroxyalkylene compounds useful in this invention. In addition, one can start with ethylene diamine or with 1,2-propylene diamine, 1,3- propylene diamine or other polyamines and then react the cyclic amidine so obtained with alkylene oxides so as to produce a terminal hydroxy group since the nitrogen bonded hydrogen on the 1-position on the ring reacts with alkylene oxides. In addition, the hydroxyalkylene group can be further oxyalkylated.

Thiol-containing compounds are prepared in a manner analogous to that employed in preparing the hydroxysubstituted cyclic amidines, for example, by employing or by employing alkylene sulfides to react With the imidazolines having an unsubstituted l-position.

Of course, it will be realized that the above compounds containing sulfur, oxygen or nitrogen can be employed as Well as any combinations of two of these elements within the same molecule, for example, cyclic amidines prepared from etc.

Thus, cyclic amidines within the scope of this invention comprise compounds of the formulae:

11 12 Where RC: and :C-R-C= are the resdues derived The only polyamines available on a large scale for'the from the carboxylic acid, monocarboxylic acids in (l) manufacture of tetrahydropyrimidines are propylene diaand (3), and dicarboxylic acids in (2), where R commine and 3,3'-iminobispropylamine. This latter product prises a hydrocarbon radical having, for example, 1-30 can be converted into the tetramine or pentamine by apcarbon atoms, hydrocarbons in which the carbon atom 5 propriate reaction with a suitable imine or by reaction chain is interrupted by oxygen, etc.; and B is a hydrogen with acrylonitrile, followed by the usual steps of convertor a hydrocarbon radical; D is hydrogen or a radical, ing the intermediate into the amine. Tetrahydropyrimifor example (AX) H where X is amino, oxygen or dines, comparable to the imidazolines of Table III ap sulfur, and A is an alkylene radical containing, for exampear in Table IV, immediately following. ple, 2-3 carbons in its main chain wherein n and x are 10 TABLE IV numbers, for example, 110 or higher, advantageously 1-3, but preferably 1, and (CB is, for example a di- 6 valent radical of the formula: 4 I

N NR

-ornom-, -o1n-orn-om- 15 I (l3HOH2, CHCH, OH-CH2CH- R CH3 CH3 CH3 CH3 Ex. No. RCOOH source of RC R In (2) CB s and the l-substituted side chain may be the b llionthic 06 1C 2 2 2 2 Same or dlfigrent; db Butyric CH CI-I CH NH; Actually, substituted cyhc amidines can be obtained gig a1cric (lHzgHzggiNm from a variety of polyamines, but only in the instance 6b Sova where one starts W1th a triamine or higher amine is there 8E28h8212 a residual group having a primary amino radical as herein Z E Z EZ required. This does not mean, however, that one could ggzggzggzggi not start with ethylene diamine or with 1,2-propylene CHZGHZCH'ZNHZ diamine. The cylic amidines so obtained could be reacted with a mole of ethylene imine or propylene imine Z Z Z so as to introduce the terminal primary amino group. CH2CH2CHzN 2 CHzCHzCHgNIIg From a practical standpoint, however, the most readily CH2CH2CH2NH, available polyamines are ethylene diamine, diethylene triaggzggiggzggz mine, triethylene tetramine, and tetraethylene pentamine. 016k, Z Z Z Z r no Undeeylenic- CHzCHzCHzNHa Howeve other polyammes hav1 a some other divalent Linoleic CHZOHZCHZNHQ fadlcal, Such as I-Iydroxy butyl CH2CH2CH2NI'I2 Methyloctadecanorc. CHzCHZCI-IQNHQ CH3 Naptheuic OHrOHzCHQNHz H Palmitic CI'I2CH2CH2NI'I2 4 The procedure employed in the manufacture of suitable 0 substituted imidazolines from dicarboxylic acids is comcan be employed.

parable to that employed when monocarboxyllc acids are Table III is limited to derivatives of the four most readily used as reactants. Suitable amines derived from the three available polyamines above indicated. amines previously noted are described in Table V.

TABLE III N N-R Ex. RCOOH source 01 RC: R No.

Laurie CHzCHzNH: Hexanoie CHzCI-IzNH; Isovaleric- CHzOHzNI-Iz Stearic CHgGH NH; Melissic- CHzCHaNH: Phenyl stearic. OHzCHzNH: Benzoic. CHzCHzNH: CIGSOtlHlG. CHzCHgNHz Naphthenim. CH2CH2NH2 i0 CHZCHZNHZ do CHQCHQNHOHgCHgNII Pelargonie. CI'IZCHQNHCHQCHQNH Lauric CHzCHzNHCHzGHzNH Palmitic CHzOHzNHOHzCHgNH Cerotic CHgCHzNHCHzCIhNI-I oTert-butyl benzoic CHzCHgNHCHzCHzNI-I p-Methoxy benzoic CI-IzCHZNHCHzCI-IQNH Toluic CHzCHzNHOHzCH NI-I Naphthenic CI-IzCH NHzCHgCHzNHg p-Hydroxy benzoic GHzOHzNHzCHgCHzNI-Ig Formic OHzCEIQNHCHzCHzNIICHzCHzNH: Methyloctadecanoic CHzCH NHCHzCH NHCHzCH NH Gapric CHzCHzNHOHzCHzNHCHzCHzNH Stearic CHZCHQNHOHQCHzNHCHzCH NH; Phenylstearic CHZCHZNHCHZCHZNHCHZCHZNH, Cresotinio CIhOHzNHCHgCHzNHCHzCIhNH; Linoleie CHzCHzNHGHgCHgNHCH CHQNH 01610 CIIzCIIzNHCI'IzCHzNHCHzCHzNIIg 3-rnethoxybenzoic CHzCHzNHCHzCHzNHCHgCHzNH: Naphthenic CHZCHZNHCHzOIhNHCHzCH NH; Laurie CHzCHzNHCHzcHzNHCHtOHzNH Benzoic CIJIICI'IQNHCI'IZCHzNHCHzCHzNHz TABLE VIII RCOOH source of RC R CHgCHzOH CHzCI-IzOH CHaCHzOH CHQCHIOH (CH3) CHzCHzOH CHQCHZOH CHCHzOI-I CHgCHzO CHaCI-IgOH CHlCHQOI'I CHCH2OH (CH5) CHzCHaOH CHQCH OH CHzCHzOH CHsCI-IzOCHzCI-IzOH -Methybenz0ic acid CHaGH OH resotinic CHZCHQOII p-Methybenzoio CHzCHzO CHzCHzOH p-tert-Butylbenzoic CHZCHiOH 3-Methoxy benzoic. GHqCHgOH Oleic CHzCHz CHzCHzOH CHzCHzOI-I Butyrie CH2CIISOCI'IZCI12OH Methyloctadecanoie CHzCHzOH Oxygen compounds analogous to those shown in tables V and VI can also be employed.

Furthermore, R can also be -(CH CH S),,H where n is ll0, but preferably 1, forming a compound analogous to the above oxygen compounds. Additionally, R can be a group containing (CH CH X),,H where X may be NH, O, S, and all three, two, or one of these elements can be present in the R grouping, for example where R is --CHzCHz N CH CH2-OH, CHzCH2SCHzCH2OH -CH2OH2SCH2CHO2CH2CI-IzNH5 and the like.

In addition, cyclic amidines of the following type can also be employed:

substituted derivatives thereof, similar or analogous compounds, etc.

Included within the scope of this invention are cyclic amidines having modified side chains, where for example the amino, hydroxyl, etc. group is acylated for example of the type N N-ornomoa etc.

Cyclic amines analogous to cyclic amidines can also be employed in this invention. As cyclic amidines are formed from reacting a fatty acid or its equivalent with a cyclic amidine forming polyamine Oxazolines are formed by reacting a fatty acid with an oxazoline forming hydroxylamine Sulfur analogues there can also be prepared II R-C OH HSOHnOHzNHn N s \c/ 1% Similarly u RGOH+NHzCH2CH2CH2OH L I \C/ is The sulfur analogue thereof is The oxazoline and thiaoxazoline can also be substituted, for example in and sulfur analogues thereof.

The R in the oxazoline and thiaoxazoline can be the same as those employed in preparing cyclic amidine. Similarly, analogous dicyclic compounds can also be prepared for example I N o 0 \Q/ \Q/ l 1;

etc.

In addition, the cyclic amidine structure may be sub- 1 7 sti tuted with other than a hydrocarbon group, for exam ple, a sulfur containing group such as wherein R is a substituted group for example, a hydrocarbon group alkyl, aryl, etc.

Imidagolidines, thiazolidines, dazolidines and their six-membered ring analogues can also be employed, for

example etc.

Additional miscellaneous amines includes the following: Hydrazine; substituted hydrazine; guanidines; substituted guanidine; polyalkyleneimine, for example polyethyleneimine, polypropyleneimine having molecular Weights of from about 400 or less to 100,000 or more; compounds of the formulae Rzhyd-rocarbon heterocyclic, etc.

Oxyalkylated amines of the type HO(AO) ANH NH (AO) ANH where A is alkylene (ethylene, propylene, butylene) and n is a number for example 1-100 or higher for example HO(EtO) EtNH NH (EtO) EtNH A wide variety of amines have been disclosed herein.

Any amine capable of forming an inorganic-amine salt 'of the oxyacid can be employed. As is quite evident, many other amines are now known and many more amines will be developed in the future. It is therefore impossible to attempt a comprehensive catalogue of all amines. However, sufficient examples have been presented herein to illustrate the wide variety of amines capable of being employed herein and to present representative examples thereof. The choice of a specific amine will depend on properties one desires in the final product, such as to solubility, use, etc.

OXYALKYLATED AMINES Also included within the scope of this invention are hydroxylamines, oxyalkylated amines, etc. For example, oxyalkylated ammonia or amines where one or more alkylene oxide units are added thereto. Examples include HN=(CH CH OH 2 NE (CH CH OH) 3 Any oxyalkylated derivatives of oxyalkylatable mono-, poly-, cyclic-, heterocyclic-, etc. amines can be oxyalkylated according to this invention to place (A), units therein, where OA represents the alkylene oxide derived radical of a unit where a can be for example 1-100, such as 1-50, for example 1-20, but preferably 1-10.

Oxyalkylated amines may be represented by the formula [(OA)nHlq where represents the amine moiety which originally contained at least one oxyalkylatable group (monoamines,

polyamines, heterocyclic amines, etc.) and (0A) has the meaning stated above. Oxyalkylation may take place at one or more positions determined by the number of oxyalkylatable positions.

Thus, any of the oxyalkylatable amines disclosed herein and elsewhere can be oxyalkylated and employed in this invention.

(OA) is derived from any suitable u, ,8 alkylene oxide, for example, alkylene oxides of the formula where R R R R are hydrogen or a substituted group, for example alkyl, cycloalkyl, aryl, etc., for example ethylene oxide, propylene oxide, butylene oxide, amylene oxide, octylene oxide, styrene oxide, methylstyrene oxide, cyclohexene oxide (where R and R are joined to form a ring), etc.

Equivalents of alkylene oxides can also be employed, for example alkylene carbonates, i.e. ethylene carbonate, propylene carbonate, butylene carbonate, etc. In addition alkylene oxides of the glycide, methyl glycide, etc. type and their equivalents can also be employed.

(OA) denotes (1) homo units for example (OEt) )n, )n, Y )n"-,

where R and R are hydrogen or a substituted radical for example alkyl, aryl, cycloalkyl, alkenyl, aralkyl, etc.

In addition, R and R can be substituted as in cases when the oxetane'is derived from pentaerythritol and derivatives thereof. Examples of such oxetanes can be found in the American Chemical Society Monogram The Pentaerythritols by Berlow et a1. (Reinhold 1958) Chapter X. Preferred embodiments of such pentaerythritol derived oxetanes are those of the formula C In (Ill-12X I out orr2 YoHg where X and Y are halogen, cyano, hydroxy and alkoxy.

The following examples are presented by way of illustration and not of limitation.

19 Example 1 To a clear solution of 10.4 g. of sodium bisulfite (0.1

mole) dissolved in 31.9 g. of water was added with stirring 21.5 g. of dimethyl dodecyl amine, Armeen DM12D 21) The solution became very thick during the addition. Heating was applied, after the completion of addition, until the solution became clear.

Example 4 (0.1 mole). The reaction was exothermic. The resulting 5 T l 1 f 5 2 f solution was clear and thick, and exhibited strong foarn- O a c ear aqueoils so H1911 O 0 so mm 1- in tq sulfite (0.05 mole) dissolved in 20 g. of water was added g ac lOIl.

14.8 g. of an 1midazoline amine (0.05 mole) denved from Example 2 laurlc acid and dipropylene triamine w1th stlrring. After of P011:lsslum d1hydr0ge11 Phosphate mole) 10 addition, a clear, yellowish solution was obtained. was dissolved in 35.1 g. of water with some warming. To this clear aqueous solution was added 21.5 g. of Armeen Example 5 i g gi g fg ig g f 211 35;? 5.2 g. of sodium bisulfate 0.05 mole) was dissolved in I 2. r k f T wa 'ogtained 25.2 g. of water. To this aqueous solution was added 7.4 unl a 0 ea 16 0am mg n s 5 g. of an imidazoline amine (0.025 mole) derived from Example 3 dipropylene triamine and lauric acid. A clear, foamy To a clear aqueous solution of 13.8 g. of sodium 131- solution was obtained. sulfate (0.1 mole) dissolved in 35.3 g. of water was added Further examples similarly prepared are tabulated with stirring 21.5 g. of Arrneen DM12D (0.1 mole). below:

TABLE IX Ex. I110rgansie1t0xyacid Moles Amine Moles 6 NaHSO CH3 1 a-N-CmHaa 7 NEHSO: 2 CH:CH1 1 N-CHr-CH:N

CHn-CH:

8 N31130:; GHQ-CH 1 /NH CH,

9 NaHSO; CH9 1 10 NRHSO; Polyethylene glycol amine 1000 HO(EtO)nEtNH1 1 11 KHQPO; "d0 l 12 KH2PO4 Polypropylene glycol amine 1000 HO(PIO)11PI'NHI 1 13 NBHSO3 CH3 1 H-(']H3 ([JH:

N N-CHz-CHNH:

14 KHQPOQ ?H3 1 H(l3--CH CH;

/N CH: CHNH;

i CisHai 15 NaHSO4 C|1H2-CHg 1 N N-CHQCHQOH 16 NaHSO Same as above 1 17 KH1PO4 Same as above 1 18 NaHSOa $113 $H-(|3Hz (EH: 1 N N-CHa-CHNH:

\ CraH21 25 USES This invention also relates to methods of using these products, which have an unexpectedly broad spectrum of uses, for example, as demulsifiers particularly for oil-in- Water emulsions; as corrosion inhibitors; as flocculants; as scale preventatives; as chelating agents or to form chelates which are themselves useful, for example, as anti-oxidants, fungicides; etc.; as flotation agents, for example, as fiotation collection agents; as additives for compositions useful in acidizing calcareous stratas of oil wells; as additives for treating water used in the secondary recovery of oil andin disposal wells; as additives used in treating oil-well strata in primary oil recovery to enhancethe flow of oil; as emulsifiers for both oil-in-water and Water-in-oil emulsions; as additives for slushing oils; as additives for cutting oils; as additives for drilling muds; as foaming agents such as foamers employed in air drilling, as agents useful in removing mud sheaths from newly drilled Wells; as dehazing or fog-inhibiting agents for fuels; as deicin-g agents for fuels; as antiseptic, preservative, bactericidal, bacteriostatic, germicidal, fungicidal agents; as agents for the textile industry, as wetting agents, as dispersing agents, as detergents, as penetrating agents, as softening agents, as dyeing assistants, as antistatic agents, and the like; as detergents useful in metal cleaners, in general cleaning, and the like; as agents useful in leather processes; as agents in metal pickling; as antifeathering agents in ink; as agents in the preparation of wood pulp and pulp slurries, as emulsifiers for insecticidal compositions and agricultural sprays such as DDT, 24-D (Toxaphene), chlordane, nicotine sulfate, hexachloracyclohexane, and the like.

The above are non-limiting examples of suitable uses for these compositions.

Having thus described my invention, what I claim as new and desire to obtain by Letters Patent is 1. The inorganic amine salt consisting of the reaction product formed by reacting 1) an alkali metal salt of phosphorous acid, phosphoric acid, sulfurous acid or sulfuric acid and (2) dimethyl dodecyl amine.

2. The inorganic amine salt of claim I wherein the alkali metal salt is sodium bisulfite.

3. The inorganic amine salt of claim 1 wherein the alkali metal salt is sodium bisulfate. 5 4. The inorganic amine salt of claim 1 wherein the alkali metal salt is potassium dihydrogen phosphate.

References Cited by the Examiner UNITED STATES PATENTS 1,701,265 2/1929 Hofmann 23-105 1,836,047 12/1931 Somerville 260583 1,860,560 5/1932 Warburton 260-579 2,118,674 5/1938 Herold et a1. 260-583 3,068,288 12/1962 Godefroi 260579 15 3,160,657 12/1964 Price et al. 260-583 X OTHER REFERENCES Beilsteins: Handbuch der Organischen Chemie, vol. 4 (Berlin, 1922), pp. 37-38 and 91-92. Conney et al.: Jour. Pharm. Exper. Therap., vol. 128,

Cooper et al.: Jour. PhaIm. Exper. Therap., vol. 114, pp. 409-410 (1955).

Hawk et al.: Practical Physiological Chemistry, 13th ed., pp. 35-37, N.Y., Blakeston, 1954.

Mark et al.: Jour. Pharm. Exper. Therap., vol. 123, pp. 70-73 (1958).

Merck Index, 7th ed., pp. 119, 403, 405, 639, 783, 794, 853, 888, and 1051, Rahway, Merck, 1960. Moeller; Inorganic Chemistry (New York, 1952), p.

533-541, and 639-648.

Schanker et al.: J our. Pharm. Exper. Therap., vol. 123, pp. 81-87 (1958).

The Dispensatory of the United States of America, 23rd ed., p. 1521, Philadelphia, Lippencott, 1943.

CHARLES E. PARKER, Primary Examiner. W. MODANCE, N. S. RIZZO Examiners.

R. L. RAYMOND, N. TROUSOF, A. D. ROLLINS,

Assistant Examiners. 

1. THE INORGANIC AMINE SALT CONSISTING OF THE REACTION PRODUCT FORMED BY REACTING (1) AN ALKALI METAL SALT OF PHOSPHOROUS ACID, PHOSPHORIC ACID, SULFUROUS ACID OR SULFURIC ACID AND (2) DIMETHYL DODECYL AMINE. 